Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations

Facile dissociation of reactants and weak binding of intermediates are key requirements for efficient and selective catalysis. However, these two variables are intimately linked in a way that does not generally allow the optimization of both properties simultaneously. By using desorption measurements in combination with high-resolution scanning tunneling microscopy, we show that individual, isolated Pd atoms in a Cu surface substantially lower the energy barrier to both hydrogen uptake on and subsequent desorption from the Cu metal surface. This facile hydrogen dissociation at Pd atom sites and weak binding to Cu allow for very selective hydrogenation of styrene and acetylene as compared with pure Cu or Pd metal alone.     

催花剂对观赏风梨丹尼斯植株体内碳水化合物代谢的影响

[目的]研究不同催花剂处理对观赏凤梨丹尼斯植株体内碳水化合物代谢的影响。[方法]以观赏凤梨丹尼斯(Guzmania‘Den-ise’)为试材,采用乙炔气体饱和溶液、浓度为400 mg/L的乙烯利溶液和电石3种催花剂对盆栽丹尼斯凤梨进行催花处理,以清水处理为对照,研究各处理丹尼斯植株体内碳水化合物代谢情况。[结果]不同催花剂处理后,丹尼斯凤梨植株体内可溶性总糖含量、淀粉含量逐渐增加,其含量水平高于对照。其中均以乙炔气体饱和溶液处理增加幅度最大。[结论]催花剂能促进观赏凤梨丹尼斯植株可溶性总糖与淀粉的积累,其中以乙炔气体饱和溶液处理增幅最大,效果最为明显。     

Ultraviolet spectrometer observations of uranus

Data from solar and stellar occultations of Uranus indicate a temperature of about 750 kelvins in the upper levels of the atmosphere (composed mostly of atomic and molecular hydrogen) and define the distributions of methane and acetylene in the lower levels. The ultraviolet spectrum of the sunlit hemisphere is dominated by emissions from atomic and molecular hydrogen, which are kmown as electroglow emissions. The energy source for these emissions is unknown, but the spectrum implies excitation by low-energy electrons (modeled with a 3-electron-volt Maxwellian energy distribution). The major energy sink for the electrons is dissociation of molecular hydrogen, producing hydrogen atoms at a rate of 10(29) per second. Approximately half the atoms have energies higher than the escape energy. The high temperature of the atmosphere, the small size of Uranus, and the number density of hydrogen atoms in the thermosphere imply an extensive thermal hydrogen corona that reduces the orbital lifetime of ring particles and biases the size distribution toward larger particles. This corona is augmented by the nonthermal hydrogen atoms associated with the electroglow. An aurora near the magnetic pole in the dark hemisphere arises from excitation of molecular hydrogen at the level where its vertical column abundance is about 10(20) per square centimeter with input power comparable to that of the sunlit electroglow (approximately 2x10(11) watts). An initial estimate of the acetylene volume mixing ratio, as judged from measurements of the far ultraviolet albedo, is about 2 x 10(-7) at a vertical column abundance of molecular hydrogen of 10(23) per square centimeter (pressure, approximately 0.3 millibar). Carbon emissions from the Uranian atmosphere were also detected.     

Epsilon carbide: a low-temperature component of interplanetary dust particles

Transmission electron microscope study of a chondritic interplanetary dust particle has revealed the presence of epsilon iron-nickel carbide, a low- temperature carbide previously encountered only in metallurgical studies. In these studies in-carbide was synthesized by carburization of iron or nickel grains in a stream of carbon monoxide or carbon monoxide plus hydrogen. Similar carburization of an iron-nickel metal in situ may have produced in-carbide during particle heating on atmospheric entry or in solar orbit. Alternatively, the epsilon-carbide may be a by-product of Fischer-Tropsch reactions in the solar nebula. Such reactions have been proposed as the mechanism of hydrocarbon formation in the early solar system.     

Toward separation and purification of olefins using dithiolene complexes: an electrochemical approach

The complex Ni[S2C2(CF3)2]2 reacts with light olefins, including ethylene and propylene, selectively and reversibly. The reaction is not poisoned by hydrogen gas, carbon monoxide, acetylene, or hydrogen sulfide, which are commonly present in olefin streams, presumably because olefin binding occurs through the sulfur ligand rather than the metal center. The reversible reaction of olefins with Ni[S2C2(CN)2]2n (n = 0, -1, -2) can be controlled electrochemically, where the oxidation state-dependent binding and release of olefins are fast on the electrochemical time scale. The observed tolerance to poisons and controllable electrochemical reactivity present an alternative approach to the separation of olefins from complex streams.     

Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene

The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts (often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional calculations were performed that identified relations in heats of adsorption of hydrocarbon molecules and fragments on metal surfaces. This analysis not only verified the facility of known catalysts but identified nickel-zinc alloys as alternatives. Experimental studies demonstrated that these alloys dispersed on an oxide support were selective for acetylene hydrogenation at low pressures.     

A new mechanism for the formation of meteoritic kerogen-like material

The carbon in ancient carbonaceous chondritic meteorites is mainly in a hydrocarbon composite similar to terrestrial kerogen, a cross-linked structure of aliphatic and aromatic hydrocarbons. Until recently, the composite has been commonly thought to have been produced in the early solar nebula by a Fischer-Tropsch-type process, involving the catalytic synthesis of hydrocarbons from carbon monoxide and hydrogen on grain surfaces. Instead, the aromatic hydrocarbons may form in gas-phase pyrolysis of simple aliphatics like acetylene and methane by a mechanism developed recently to explain formation of soot in combustion and of aromatic molecules in circumstellar envelopes. Nonequilibrium chemical kinetic calculations indicate that this mechanism can produce meteoritic aromatics if the initial concentration of simple hydrocarbons in the solar nebula was sufficiently but not unreasonably high.     

Supramolecular Archimedean cages assembled with 72 hydrogen bonds

Self-assembly of multiple components into well-defined and predictable structures remains one of the foremost challenges in chemistry. Here, we report on the rational design of a supramolecular cage assembled from 20 ions of three distinct species through 72 hydrogen bonds. The cage is constructed from two kinds of hexagonal molecular tiles, a tris(guanidinium)nitrate cluster and a hexa(4-sulfonatophenyl)benzene, joined at their edges through complementary and metrically matched N-H···O-S hydrogen bonds to form a truncated octahedron, one of the Archimedean polyhedra. The truncated octahedron, with an interior volume of 2200 cubic angstroms, serves as the composite building unit of a body-centered cubic zeolite-like framework, which exhibits an ability to encapsulate a wide range of differently charged species, including organic molecules, transition metal complexes, and "ship-in-a-bottle" nanoclusters not observed otherwise.     

Platinum-like behavior of tungsten carbide in surface catalysis

Tungsten carbide catalyzes the formation of water from hydrogen and oxygen at room temperature, the reduction of tungsten trioxide by hydrogen in the presence of water, and the isomerization of 2,2-dimethylpropane to 2-methylbutane. This catalytic behavior, which is typical of platinum, is not exhibited at all by tungsten. The surface electronic properties of the latter are therefore modified by carbon in such a way that they resemble those of platinum.     

苯与过氧化氢直接催化氧化合成苯酚

研究苯一步催化氧化合成苯酚的新方法，以Ｆｅ－Ｃｕ－Ｍｎ－Ｏ／海泡石为催化剂，双氧水及添加剂为氧化剂。探讨添加剂性质、催化反应温度及双氧水浓度对反应过程的影响规律，并提出催化氧化的反应机理。     

Solid state electrodes for high energy batteries

A new class of electrode materials for high energy density, rechargeable batteries based on topochemical reactions of lithium and transition metal compounds is evolving. The physical and structural properties relevant to the ability of transition metal oxides with framework structures to topochemically incorporate lithium are discussed. Perovskite-related structures are particularly attractive hosts for lithium.     

The Cassini UVIS stellar probe of the Titan atmosphere

The Cassini Ultraviolet Imaging Spectrometer (UVIS) observed the extinction of photons from two stars by the atmosphere of Titan during the Titan flyby. Six species were identified and measured: methane, acetylene, ethylene, ethane, diacetylene, and hydrogen cyanide. The observations cover altitudes from 450 to 1600 kilometers above the surface. A mesopause is inferred from extraction of the temperature structure of methane, located at 615 km with a temperature minimum of 114 kelvin. The asymptotic kinetic temperature at the top of the atmosphere determined from this experiment is 151 kelvin. The higher order hydrocarbons and hydrogen cyanide peak sharply in abundance and are undetectable below altitudes ranging from 750 to 600 km, leaving methane as the only identifiable carbonaceous molecule in this experiment below 600 km.     

醚菊酯中间体β,β-二甲基苯乙醇的制备

[目的]以溴苯为起始原料,经格式反应制备β,β-二甲基苯乙醇（c）。[方法]以溴苯为起始原料制备α,α-二甲基苄醇（a）,再以氯化亚砜为氯代试剂,由a制备α,α-二甲基氯化苄（b）。最后再通过（b）制备的格氏试剂与多聚甲醛反应,制备目标化合物——β,β-二甲基苯乙醇（c）。[结果]该制备方法可较好的制备目标化合物,收率达64.7%。[结论]此合成路线原料易得,工艺简单,收率较好。     

Carbon-14 Dating with the Liquid Scintillation Counter: Total Synthesis of the Benzene Solvent

Samples are analyzed for natural radiocarbon content by a total synthesis of benzene from their organic constituents. The benzene is employed as the solvent in a liquid scintillation counter. The instrument used permits 15grams of carbon to be counted with an efficiency of 40 percent and a background of 13 counts per minute.     

Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites

The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.     

Ni／海泡石催化苯选择加氢为环己烯研究

研制和采用Ｎｉ／海泡石为催化剂，使苯气固相选择加氢为环己烯，分析了此过程的热力学和动力学特性，考察了液苯空速、氢本比、反应和修饰剂对过程的影响规律，确定了苯部分加氢制环己烯的优化条件，修饰剂对选择性中氢有重要影响，以水为修饰剂时，取得卖座经率８０％和环己烯选择性３７．９％的结果。     

Superconductivity in dense lithium

Superconductivity in compressed lithium is observed by magnetic susceptibility and electrical resistivity measurements. A superconducting critical temperature (Tc) is found ranging from 9 to 16 kelvin at 23 to 80 gigapascals. The pressure dependence of Tc suggests multiple phase transitions, consistent with theoretical predictions and reported x-ray diffraction results. The observed values for Tc are much lower than those theoretically predicted, indicating that more sophisticated theoretical treatments similar to those proposed for metallic hydrogen may be required to understand superconductivity in dense phases of lithium.     

Formation of Hardening Coatings for Working Elements of Agricultural Machines When Combining the High-Frequency Heating and High-Temperature Synthesis of the Materials

A method of surfacing of a wide range of cast, hard, wear-resistant materials on a steel base was created based on the performed investigations. The surfacing was carried out in the conditions of heating with high-frequency currents (HFCs). The exothermic thermite mixtures were used, including the mixtures of metal oxides, aluminum, or silicon. In the course of synthesis, the coatings with the weld pad of 100–900 μm were obtained. The surfacing process was carried out in two main synthesis modes—high and low-temperature using the exothermic thermite mixtures—and allowed extending significantly the raw material base of the surfacing materials, including refusing the use of the traditional surfacing eutectic alloys and charge mixtures with the boron carbide for deep borating. It is shown that the synthesis of the coating of the exothermic thermite mixture FeO/B₂O₃/Si is identical to the diffusion saturation of the surface layer with the classical mode of borating during the HFC-heating.     

载体活性炭的研制(Ⅰ)——松根炭制维尼纶载体炭

本研究以松根炭为原料,利用新研制的粘合剂——复合1~#和复合2~#,制成乙炔气相沸腾床合成醋酸乙烯(维尼纶中间品)催化剂载体活性炭。产品醋酸吸附值为566mg/g、强度(球磨法)71.7％,可替代椰壳、果壳(核)等高强度活性炭。     

Ultraviolet spectrometer observations of neptune and triton

Results from the occultation of the sun by Neptune imply a temperature of 750 +/- 150 kelvins in the upper levels of the atmosphere (composed mostly of atomic and molecular hydrogen) and define the distributions of methane, acetylene, and ethane at lower levels. The ultraviolet spectrum of the sunlit atmosphere of Neptune resembles the spectra of the Jupiter, Saturn, and Uranus atmospheres in that it is dominated by the emissions of H Lyman alpha (340 +/- 20 rayleighs) and molecular hydrogen. The extreme ultraviolet emissions in the range from 800 to 1100 angstroms at the four planets visited by Voyager scale approximately as the inverse square of their heliocentric distances. Weak auroral emissions have been tentatively identified on the night side of Neptune. Airglow and occultation observations of Triton's atmosphere show that it is composed mainly of molecular nitrogen, with a trace of methane near the surface. The temperature of Triton's upper atmosphere is 95 +/- 5 kelvins, and the surface pressure is roughly 14 microbars.